Electronic isomers in [(CO2)nROH]− cluster anions. II. Ab initio calculations

摘要: Ab initio MO calculations have been performed for the [(CO2)nROH]− (R=H and CH3) anions with n=1 2. Three stable structures are found [(CO2)H2O]−, two [(CO2)CH3OH]−. All [(CO2)ROH]− characterized by charge localization on CO2 moiety, which interacts ROH through an O–H⋯O linkage. It is also revealed that addition of to CO2− leads formation a potential barrier against autodetachment higher than bare CO2−, results in increasing stability species. For n=2 predict existence types isomers having different degrees excess electron localization: CO2−⋅ROH(CO2) C2O4−⋅ROH isomers. These “electronic isomers” calculated be close energy, while their vertical detachment energies (VDEs) differ more 1 eV. The ab discussed comparison recent experimental ones derived from photoelectron spectra [(CO2)nROH]−.